CN102806104B - Catalyst for aqueous-phase preparation of indole nitrogen arylide and preparation method of indole nitrogen arylide - Google Patents
Catalyst for aqueous-phase preparation of indole nitrogen arylide and preparation method of indole nitrogen arylide Download PDFInfo
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Abstract
The invention discloses a catalyst for aqueous-phase preparation of indole nitrogen arylide. The catalyst comprises oxides of copper salt or copper, ligands and surface active agents according to the molar ratio of 1:(0.5-50):(0.5-50). The invention further discloses a method utilizing the catalyst to realize aqueous-phase preparation of the indole nitrogen arylide. The method includes steps of adding the catalyst, indoles or indole derivatives, iodo-arylide and alkali into water to realize nitrogen arylation reaction; and treating after the nitrogen arylation reaction so as to obtain the indole nitrogen arylide. The catalyst for the aqueous-phase preparation of the indole nitrogen arylide is cheap and environment-friendly, is simple in composition, wide in application range and easy to use, and can be used for industrialization production. Reaction conditions required by the catalyst for preparing the indole nitrogen arylide are easy to control.
Description
Technical field
The present invention relates to metal organic catalysis synthesis technical field, specifically relate to catalyst and method that a kind of aqueous phase prepares indole nitrogen arylide.
Background technology
The current whole world starts to enter the green economy epoch, and in 2009, just holding council specially advocated development green economy in the United Nations, advocated green new policies.Meanwhile, countries in the world actively propose various economic revival plan, promote green economy development.The countries such as the U.S., Korea S, Japan, European Union propose development plan, and European Union has also made positive deployment, national economy development plan, Korea S even directly calls that low-carbon green increases, and other developing country have also been made corresponding planning.China is also very positive in the process, and reply global financial crisis is regarded as the new opportunities promoting economic development, for economic crisis and environmental crisis seek common reply way.State Environmental Protection Administration puts into effect " environmental impact assessment public participation Tentative Measures " in March, 2006, has issued in April, 2007 " measures for the disclosure of environmental information (trying) ".Play execution " environmental administrative punishment way (People's Republic of China's Environmental Protection Department makes No. 8) " on March 1st, 2010; " local environment quality standard and pollutant emission standard put on record management method (People's Republic of China's Environmental Protection Department makes No. 9) ", the General Office of the State Council has issued " instruction about advancing the work of atmosphere pollution groupcontrol to improve region air quality " in May, 2010.Meanwhile, in September, 2008, General Office, the People's Government of Zhejiang Province issued " improving some suggestions of environmental impact assessment examination and approval system about further specification ".
Green Chemistry is as green economy core component, its objective is from source and reduce and pollution abatement, because the usual consumption of solvent in chemical reaction is maximum, therefore a current research emphasis how to adopt nontoxic solvent (Li Chaojun, Chen Deheng, Wang Dong, Liu Li, Chen Yongjun: " aqueous phase organic reaction complete works of ", in August, 2009 first edition).In modern organic reaction, the most frequently used reaction medium is that the virose volatile organic solvent of tool is as oxolane, toluene, carrene etc.Poorly soluble in water of most of organic compound, a lot of metal reagent can decompose in water, therefore generally avoids using water as reaction medium.But all vital movements are all carried out in water, water has unrivaled advantage as chemical reaction solvent: cost is minimum, chemical physical property is stable, nonhazardous, is the natural selection of environment-friendly reaction.And between water and reaction molecular, there is distinctive interaction, provide the broad space of development novel synthesis.
The nearest more than ten years, aqueous phase organic reaction research has had breakthrough, organic chemical reactions in a large amount of aqueous medium is developed, such as " chemistry waterborne " reaction of new chemical phenomenon is found (Li Chaojun, Chen Deheng, Wang Dong, Liu Li, Chen Yongjun: " aqueous phase organic reaction complete works of ", in August, 2009 first edition).Breslow in 1980 etc. find the cycloaddition reaction of cyclopentadiene and ethylene methacrylic ketone in water than fast 700 times (Darryl C.Rideout, Ronald Breslow:J.Am.Chem.Soc.1980,102,7816-7817) in isopropyl alkane.Fujimoto in 2000 etc. find in the free radical cyclization caused at Et3B and micro-O2, if make solvent with hexane or benzene, only have accessory substance to generate, but productive rate can reach 67-78% (Hideki Yorimitsu, Tomoaki Nakamura when reaction is carried out in aqueous phase, Hiroshi Shinokubo, Koichiro Oshima, Kiyoyuki Omoto, Hiroshi Fujimoto:J.Am.Chem.Soc.2000,122,11041-11047).In aqueous metal catalyzed coupling reaction, Zhang in 2007 etc. achieve room temperature aqueous phase Suzuki coupling reaction (Shenghai Li, Yingjie Lin with guanidine as part, Jungang Cao, Suobo Zhang:J.Org.Chem.2007,72,4067-4072).Plenio in 2008 etc. achieve Sonogashira coupling reaction (the Christoph A.Fleckenstein of heterocycle halides with water and isopropyl alcohol as solvent with water-soluble Pd complex, Herbert Plenio:Green Chem.2008,10,563-570).Tsai in 2009 etc. can repeat catalytic coupling (Shao-Nung Chen with the aqueous phase that cationic bipyridyl achieves end-group alkyne as part, Wei-Yi Wu, Fu-Yu Tsai:Green Chem.2009, 11, 269-274), the Microwave Assisted Process such as Vanelle achieves thiazole aqueous phase Suzuki coupling reaction (Anita Cohen, Maxime D.Crozet, Pascal Rathelot, Patrice Vanelle:Green Chem.2009, 11, 1736-1742), the 2-aminophenyl diphenylphosphinite such as Firouzabadi achieves aqueous phase Heck coupling reaction (Habib Firouzabadi as part, Nasser Iranpoor, Mohammad Gholinejad:Tetrahedron 2009, 65, 7079-7084).(Kevin H.Shaughnessy:Chem.Rev.2009,109,643-710) that these aqueous metal catalytic reactions realize mainly through designing various water-soluble metal part.
Indole nitrogen arylated compound is class purposes compound more widely, such as document (Anovel class of " GABAergic " agents:1-aryl-3-(aminoalkylidene) oxindoles, Journal of Medicinal Chemistryl (989), 32 (2), 437-44) report that indole nitrogen is used for synthesis to methoxybenzene and has bioactive 1-aryl-3-(amino alkylidene) indolone (1-aryl-3-(aminoalkylidene) oxindoles).Document 1 (Directed synthesis and immunoactive properties of (2-hydroxyethyl) ammonium salts of 1-R-indol-3-ylsulfanyl (sulfonyl) alkanecarboxylic acids, Russian Chemical Bulletin (2010), 59 (12), 2236-2246), document 2 (Rearrangement of 1-arylindoles to 5H-dibenz [b, f] azepines, Tetrahedron (1995), 51 (7), 2091-8) and document 3 (Palladium-Catalyzed Indole, Pyrrole, and Furan Arylation by Aryl Chlorides, Journal of Organic Chemistry (2011), 76 (2), 471-483) report respectively with indole nitrogen p-nitrophenyl respectively, indole nitrogen synthesizes as substrate the method that other have bioactive compound or synthesis of indole derivative to chlorobenzene and 3-methyl indol pyridine.The method of the synthesis above-claimed cpd of developing green is significant.The indole nitrogen arylation of organic phase is very ripe, but the indole nitrogen arylation of aqueous phase does not also have effective catalyst
At present, for nitrogen arylation reaction, go back the aqueous synthesis method that neither one is perfect so far.This reaction is metal catalytic carbonnitrogen bond formation method the most powerful at present, can prepare various nitrogen heterocyclic ring analog and aromatic amine ((a) Buchwald, S.L.; Mauger, C.; Mignani, G.; Scholzc, U.Adv.Synth.Catal.2006,348,23. (b) Hartwig, J.F.Synlett.2006,9,1283. (c) Muci, A.R.; Buchwald, S.L.In Topics in Current Chemistry, 2002; Vol.219, pp 131. (d) Hartwig, J.F.Comprehensive Coordination Chemistry II 2004,9,369. (e) Schlummer, B.; Scholz, U.Adv.Synth.Catal.2004,346,1599. (f) Zhang, H.; Cai, Q.; Ma, D.J.Org.Chem.2005,70,5164).Owing to having biologically active widely containing nitrogen compound especially nitrogen heterocyclic ring, this reaction is made to have very important value in chemistry, pharmacy, biology.But these reactions are substantially all carried out in toluene, are therefore transplanted in water by this reaction, can promote chemical pharmacy industry Green Process effectively.
Summary of the invention
The invention provides the catalyst that a kind of aqueous phase prepares indole nitrogen arylide, this catalyst environmental friendliness, composition are simple, low price and easy to use, can be prepared the indole nitrogen arylide having various functional group and replace type by this catalyst.
Present invention also offers the method that above-mentioned catalyst is utilizing aqueous synthesis method to prepare indole nitrogen arylide, this application process is implemented simple, and reaction condition is easy to control, and can be used for suitability for industrialized production.
Aqueous phase prepares a catalyst for indole nitrogen arylide, comprising: the oxide of mantoquita or copper, part and surfactant, the mol ratio of described mantoquita or the oxide of copper, part and surfactant is 1: 0.5-50: 0.5-50.
In above-mentioned catalyst, described mantoquita is common cuprous salt or cupric salt, and the oxide of described copper is cupric oxide or cuprous oxide; Described cuprous salt comprise in cuprous iodide, stannous chloride, cuprous bromide, copper fluoride one or more; Described cupric salt comprises at least one in copper sulphate, copper nitrate, cupric iodide, copper chloride, copper bromide, copper fluoride.
Described part is at least one in bipyridyl or dipyridyl derivatives, ethylenediamine or ethylene diamine derivative, cyclohexanediamine or cyclohexanediamine derivative, propanedione or propanedione derivative, proline or proline derivative.Described bipyridyl or dipyridyl derivatives comprise 2,2 '-bipyridyl, 2,2 '-bipyridyl-4,4 '-dioctyl phthalate, 4,4 '-dimethyl-2,2 '-bipyridyl etc.; Described ethylenediamine or ethylene diamine derivative comprise ethylenediamine, N, N '-dimethyl-ethylenediamine etc.; Described cyclohexanediamine or cyclohexanediamine derivative comprise 1,2-cyclohexanediamine, N, N '-dimethyl-1,2-cyclohexanediamine etc.; Described propanedione or propanedione derivative comprise propanedione, 2,2,6,6-tetramethyl-3,5-heptadione, 1,3-diphenylprop diketone, 2-acetyl cyclohexanone etc.
Described surfactant comprises at least one in anion surfactant, cationic surfactant, non-ionic surface active agent or zwitterionic surfactant etc.As further preferred, described surfactant comprises at least one in neopelex, lauryl sodium sulfate, Choline Chloride, n-butyl, dodecyl ammonium salt, cetyl ammonium salt, dococylpyridinium ammonium salt, cetyl pyridinium ammonium salt, department class, tween, APG, sugar ester, betaine, imidazoline etc.Experiment shows, in above-mentioned three kinds of surfactants, amphoteric surfactant effect is best, and cationic surfactant effect is taken second place.
General aqueous catalysis reaction realizes high efficiency catalysis with water miscible part, and part is expensive.And the present invention is by the synergistic function of surfactant, facilitate the contacting efficiency of catalyst and reagent, only need with common part, just can realize high efficiency aqueous phase indole nitrogen arylation.Experiment proves these DDTCs, part to be directly used in aqueous phase, poor effect.
Aqueous phase prepares a method for indole nitrogen arylide, comprising: catalyst, indoles or indole derivatives, iodo aryl compound and alkali are added to the water, carry out nitrogen arylation reaction, and after having reacted, post processing obtains indole nitrogen arylide; Described catalyst comprises the oxide of mantoquita or copper, part and surfactant, and the mol ratio of described mantoquita or the oxide of copper, part and surfactant is 1: 0.5-50: 0.5-50.Its course of reaction is shown below:
In above formula, described R
1be selected from hydrogen atom or C
1-C
4alkyl; Described R
2select hydrogen atom, alkoxyl, halogen or nitro.For reducing preparation cost, preferred indoles or indole derivatives are indoles or 3-methyl indol; Described iodo aryl compound is preferably to methoxyl group iodobenzene, to nitro iodobenzene, in chlorine iodobenzene or iodobenzene.
For ensureing carrying out fast smoothly of reaction, the temperature of described nitrogen arylation reaction is 50-130 degree Celsius.The most frequently used temperature is 60-100 degree Celsius.The too high control being unfavorable for reacting of temperature, the too low then reaction speed of temperature is comparatively slow, and preparation cost is higher.
The mol ratio of described indoles or indole derivatives, iodo aryl, alkali and catalyst is 1: 0.5-50: 0.5-50: 0.5-50.Ensureing under the precondition that indoles or indole derivatives react completely as far as possible, for avoiding wastage of material, the mol ratio of described indoles or indole derivatives, iodo aryl, alkali and catalyst is 1: 1-2: 1-4: 0.05-0.5, and wherein catalyst calculates with the mol ratio of wherein copper.In described catalyst, the kind of the oxide of mantoquita or copper, part and surfactant is with aforementioned.
Described alkali can select conventional organic base or inorganic base, and preferred alkali comprises at least one in potash, potassium phosphate, sodium carbonate, NaOH, potassium hydroxide, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide, caustic alcohol etc.
For reducing operation easier, be convenient to realize industrialization, consider the chemical property of object product simultaneously, preferred post-processing approach comprises:
(1) joined by organic solvent in the reaction system after having reacted, extraction indole nitrogen arylide is in organic phase;
(2) organic phase after extraction is concentrated, obtain indole nitrogen arylide sterling through chromatographic isolation.
In above-mentioned last handling process, described organic solvent is all have solvent compared with highly dissoluble to indole nitrogen arylide, comprises at least one in ethyl acetate, ether, chloroform, carrene, benzinum, n-hexane, t-butyl methyl ether.
Above-mentioned aqueous phase is prepared in the method for indole nitrogen arylide, and the addition of water can adjust according to actual needs, and the addition of general indoles or indole derivatives is 0.1-0.5mol/ml with the molal volume ratio of the addition of water, is not strict with.
The present invention has the following advantages and effect relative to prior art tool:
(1) catalyst of the present invention is that common chemical reagent forms simply, low price, use cost are low.
(2) when catalyst of the present invention uses, with water as solvent, avoid organic solvent and use, environmental protection.
(3) catalyst of the present invention is applied widely, with multiple functional group and can replace type compatibility.
(4) aqueous phase of the present invention prepares the method for indole nitrogen arylide, and reaction condition is easy to control, and products collection efficiency is high, can be used for suitability for industrialized production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
By cuprous iodide (8 milligrams, 0.04 mM), 2,2 '-bipyridyl (12 milligrams, 0.08 mM), betaine (94 milligrams, 0.8 mM), tripotassium phosphate (170 milligrams, 0.8 mM), indoles (47 milligrams, 0.4 mM), insert in reaction bulb to methoxyl group iodobenzene (187 milligrams, 0.8 mM), add 2 ml waters, be heated to 90 degrees Celsius, react 10 hours.Chloroform is joined in reaction system, use chloroform extraction product, be separated with silica gel chromatograph after concentrated and obtain indole nitrogen to methoxybenzene 72 milligrams, productive rate 81%.
Indole nitrogen is to the nuclear magnetic resonance data of methoxybenzene:
1h NMR (500MHz, CDCl
3) δ 7.67 (d, J=8.0Hz, 1H), 7.45 (d, J=8.0Hz, 1H), 7.40 (d, J=9.0Hz, 2H), 7.27 (d, J=3.5,1H), 7.20 (t, J=8.0,1H), 7.14 (t, J=8.0,1H), 7.02 (d, J=9.0,2H), 6.64 (d, J=3.5,1H), 3.87 (s, 3H).
Embodiment 2
By cuprous iodide (8 milligrams, 0.04 mM), 2,2 '-bipyridyl (12 milligrams, 0.08 mM), betaine (94 milligrams, 0.8 mM), tripotassium phosphate (170 milligrams, 0.8 mM), indoles (47 milligrams, 0.4 mM), insert in reaction bulb to nitro iodobenzene (199 milligrams, 0.8 mM), add 2 ml waters, be heated to 90 degrees Celsius, react 10 hours.Chloroform is joined in reaction system, use chloroform extraction product, be separated with silica gel chromatograph after concentrated and obtain indole nitrogen p-nitrophenyl 90 milligrams, productive rate 95%.
The nuclear magnetic resonance data of indole nitrogen p-nitrophenyl:
1h NMR (500MHz, CDCl
3) δ 8.42-8.37 (m, 2H), 7.72-7.64 (m, 4H), 7.37 (d, J=3.5Hz, 1H), 7.32-7.21 (m, 2H), 6.76 (d, J=3.5Hz, 1H).
Embodiment 3
By cuprous iodide (8 milligrams, 0.04 mM), 2,2 '-bipyridyl (12 milligrams, 0.08 mM), betaine (94 milligrams, 0.8 mM), tripotassium phosphate (170 milligrams, 0.8 mM), indoles (47 milligrams, 0.4 mM), insert in reaction bulb to chlorine iodobenzene (191 milligrams, 0.8 mM), add 2 ml waters, be heated to 90 degrees Celsius, react 10 hours.Chloroform is joined in reaction system, use chloroform extraction product, be separated with silica gel chromatograph after concentrated and obtain indole nitrogen to chlorobenzene 74 milligrams, productive rate 82%.
Indole nitrogen is to the nuclear magnetic resonance data of chlorobenzene:
1h NMR (500MHz, CDCl
3) δ 7.68 (d, J=8.0Hz, 1H), 7.52-7.41 (m, 5H), 7.28 (d, J=3.0Hz, 1H), 7.25-7.15 (m, 2H), 6.68 (d, J=3.0Hz, 1H).
Embodiment 4
By cuprous iodide (8 milligrams, 0.04 mM), 2,2 '-bipyridyl (12 milligrams, 0.08 mM), betaine (94 milligrams, 0.8 mM), tripotassium phosphate (170 milligrams, 0.8 mM), 3-methyl indol (52 milligrams, 0.4 mM), iodobenzene (163 milligrams, 0.8 mM) inserts in reaction bulb, adds 2 ml waters, be heated to 90 degrees Celsius, react 10 hours.Chloroform is joined in reaction system, use chloroform extraction product, be separated with silica gel chromatograph after concentrated and obtain 3-methyl indol pyridine 65 milligrams, productive rate 78%.
The nuclear magnetic resonance data of 3-methyl indol pyridine:
1h NMR (500MHz, CDCl
3) δ 7.62 (d, J=Hz, 1H), 7.55 (d, J=Hz, 1H), 7.51-7.46 (m, 3H), 7.34-7.28 (m, 2H), 7.25-7.12 (m, 3H), 2.39 (s, 3H).
Embodiment 5
Be that mantoquita adopts stannous chloride (4 milligrams, 0.04 mM) with embodiment 2 condition difference, part adopts 1,2-cyclohexanediamine (14 milligrams, 0.12 mM), other conditions are with embodiment 2, prepare indole nitrogen p-nitrophenyl 86 milligrams, productive rate 90%.
Embodiment 6
Be that mantoquita adopts (6 milligrams, cuprous oxide with embodiment 4 condition difference, 0.04 mM), alkali adopt (7 milligrams, potassium hydroxide, 0.12 mM), reaction temperature is 100 degrees Celsius, react 12 hours, utilize t-butyl methyl ether extraction product after reaction, other conditions are with embodiment 2, finally obtain 3-methyl indol pyridine 62 milligrams, productive rate is 75%.
Embodiment 7
Be that mantoquita adopts cuprous bromide (11 milligrams with embodiment 2 condition difference, 0.08 mM), part adopts N, N '-dimethyl-1,2-cyclohexanediamine (34 milligrams, 0.24 mM), surfactant adopts softex kw (44 milligrams, 0.12 mM), and other conditions are with embodiment 2, prepare indole nitrogen p-nitrophenyl 88 milligrams, productive rate 92%.
Embodiment 8
Be that mantoquita adopts copper chloride (14 milligrams, 0.08 mM) with embodiment 2 condition difference, other conditions, with embodiment 2, prepare indole nitrogen p-nitrophenyl 74 milligrams, productive rate 78%.
Embodiment 9
Be with embodiment 1 condition difference, part adopts N, N '-dimethyl-ethylenediamine (4 milligrams, 0.04 mM), surfactant adopts Tween 80 (342 milligrams, 0.8 mM), reaction temperature is 80 degrees Celsius, and the reaction time is 14 hours, and other conditions are with embodiment 1, finally obtain indole nitrogen to methoxybenzene 67 milligrams, productive rate 75%.
Embodiment 10
Be with embodiment 2 condition difference, part adopts 2,2,6,6-tetramethyl-3,5-heptadione (15 milligrams, 0.08 mM), surfactant adopts neopelex (278 milligrams, 0.8 mM), and alkali selects (32 milligrams, NaOH, 0.8 mM), other conditions, with embodiment 2, finally prepare indole nitrogen p-nitrophenyl 81 milligrams, productive rate 65%.
Comparative example 1
By cuprous iodide (8 milligrams, 0.04 mM), 2,2 '-bipyridyl (12 milligrams, 0.08 mM), tripotassium phosphate (170 milligrams, 0.8 mM), indoles (47 milligrams, 0.4 mM), to methoxyl group iodobenzene (187 milligrams, 0.8 mM) insert in reaction bulb, add 2 ml waters, be heated to 90 degrees Celsius, react 10 hours.Chloroform is joined in reaction system, use chloroform extraction product, be separated with silica gel chromatograph after concentrated and obtain indole nitrogen to methoxybenzene 8 milligrams, productive rate 9%.
Claims (2)
1. aqueous phase prepares a catalyst for indole nitrogen arylide, it is characterized in that, it consists of: cuprous iodide 8 milligrams, 2,2'-bipyridyl 12 milligrams, betaine 94 milligrams.
2. aqueous phase prepares a method for indole nitrogen arylide, comprising:
By cuprous iodide 8 milligrams, 2,2'-bipyridyl 12 milligrams, betaine 94 milligrams, tripotassium phosphate 170 milligrams, indoles 47 milligrams, insert in reaction bulb to nitro iodobenzene 199 milligrams, add 2 ml waters, be heated to 90 degrees Celsius, react 10 hours; Chloroform is joined in reaction system, use chloroform extraction product, be separated with silica gel chromatograph after concentrated and obtain indole nitrogen p-nitrophenyl 90 milligrams.
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| CN1863752A (en) * | 2002-08-02 | 2006-11-15 | 罗迪亚药业公司 | Copper catalyzed arylation |
| CN101691318A (en) * | 2009-06-29 | 2010-04-07 | 中山大学 | N-arylation method taking substituted adipic dihydrazide as ligand in aqueous phase system |
| CN101774874A (en) * | 2010-01-25 | 2010-07-14 | 中山大学 | N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system |
| WO2012084857A2 (en) * | 2010-12-21 | 2012-06-28 | Bayer Cropscience Ag | Method for producing 2-(triazinylcarbonyl) sulfonanilides |
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| CN1863752A (en) * | 2002-08-02 | 2006-11-15 | 罗迪亚药业公司 | Copper catalyzed arylation |
| CN101691318A (en) * | 2009-06-29 | 2010-04-07 | 中山大学 | N-arylation method taking substituted adipic dihydrazide as ligand in aqueous phase system |
| CN101774874A (en) * | 2010-01-25 | 2010-07-14 | 中山大学 | N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system |
| WO2012084857A2 (en) * | 2010-12-21 | 2012-06-28 | Bayer Cropscience Ag | Method for producing 2-(triazinylcarbonyl) sulfonanilides |
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